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Background: Plastic is one of the most widely used materials worldwide in various fields, including packaging and agriculture. Its large quantities require proper disposal and for this reason more and more attention is paid to the issue of degrading plastic. Thanks to the production of non-specific enzymes, fungi are able to attack complex and recalcitrant xenobiotics such as plastics. In recent years, several spectroscopic methods were used to study the plastic degradation ability of different fungal species. Among these, Fourier transform infrared (FT-IR) and FT-Raman spectroscopy techniques are the most used. Surface-enhanced Raman scattering (SERS) spectroscopy is a powerful technique which uses metal nanoparticles (NPs) to enhance the Raman signal of molecules adsorbed on the NPs surface. In this work, the isolation of different fungi from field-collected plastic debris and the ability of these isolates to growth and colonizing the low-density polyethylene (LDPE) were explored by using scanning electron microscope (SEM), attenuated total reflectance-Fourier transform infrared (ATR-FTIR) and SERS spectroscopies. Results: Forty-seven fungal isolates belonging to 10 genera were obtained; among them only 11 were able to grow and colonize the LDPE film. However, after 90 days trial, only one isolate of Cladosporium cladosporioides (Clc/1) was able to carry out the initial degradation of the LDPE film. In particular, based on SEM observations, small cavities and depressed areas of circular shape were visible in the treated samples. Additionally, ATR-FTIR, normal Raman and SERS analyses supported the structural changes observed via SEM. Notably, ATR-FTIR and normal Raman spectra showed a significant decrease in the relative intensity of the methylene group bands. Similarly, the SERS spectra of LDPE after the fungal attack, confirmed the decrease of methylene groups bands and the appearance of other bands referring to LDPE polyphenolic admixtures. Conclusions: These re

In the last decades, the number of studies about the valorization of agricultural by-products has strongly increased due to the growing focus on the circular economy. In this context, mushroom cultivation is raising attention for its nutritional properties and adaptability to different growing conditions. The goal of this project is, therefore, to create a link between two production chains, valorizing the solid anaerobic digestate fraction from the biogas plant as a potential substrate for Pleurotus ostreatus full-scale cultivation. A preliminary in vitro trial shows that the mycelia can colonize at the same rate in both the conventional substrate, which was wheat straw added with sunflower cake and the experimental ones supplemented with corn digestate. The most important and innovative part of the work was full-scale cultivation. Quantitative analyses demonstrate that P. ostreatus is capable of growing on the conventional substrate as well as on the substrate containing 15% of digestate without reducing the mushroom harvest. Even better, digestate seems to stimulate a precocious and more homogeneous production. Chemical and spectroscopic analyses on the fruiting bodies confirm the results; in fact, mushrooms show a comparable structural composition, highlighted with FTIR and SERS spectroscopic evaluations. Moreover, the nutrient content did not change due to the addition of digestate. These promising results demonstrate that anaerobic digestate can become a resource for P. ostreatus cultivation without production losses and maintaining the same qualitative characteristics.

In this work, we have developed a simple method to carry out the quantitative analysis of deethylhydroxyatrazine (DEHA), the most abundant metabolite of atrazine herbicide (ATZ), based on the surface-enhanced Raman scattering technique. Since this ATZ product can undergo pH-dependent tautomerization, a previous characterization of the DEHA vibrational spectrum was accomplished. This study consisted of the Raman scattering study, both experimental and theoretical, of the enolic and ketonic tautomers of this molecule. SERS spectra were recorded at different pH in order to assess the effect of the metal surface in nanoparticles along with the pH on the structure of DEHA and to find the optimal experimental conditions of the quantitative detection of DEHA. Additionally, the interaction of DEHA with two types of humic acid reference standards, the Elliot humic and leonardite humic ones, was also performed by SERS. This interaction was conducted with two different objectives: to evaluate the interaction mechanism of the ATZ degradation product with humic substances and to check if this interaction can modify the sensitivity of the SERS detection of DEHA. The results presented in this study have clearly demonstrated that SERS spectroscopy is a very powerful technique for characterizing DEHA and other triazine sub-products at a very low concentration in water and also for analyzing the interaction of these important pollutants with humic substances.

Significant benefit of soil organic matter (SOM) to crop productivity is scientifically well documented. The main constituents and active fractions of SOM are humic substances (HS) and phenolic compounds. Since both these two components strongly impact plant-soil relationship, it is importantly from an ecological point of view to discriminate their biological effects and relating them to their composition. In this study we compared the biological effects of HS, and the soil water soluble phenols (SWSP) on growth, antioxidant activities, carbohydrates, proteins, phenols, and vitamins of Pinus laricio callus. Each extract was assessed for the content of low molecular weight organic acids, soluble carbohydrates, fatty acids, and phenolic acids. Moreover, Fourier transform infrared (FT-IR) and surface-enhanced Raman scattering (SERS) spectroscopies were applied to study their molecular structure. The results showed that HS produced better callus growth compared to the control and SWSP. Carbohydrates decreased in presence of HS while proteins, vitamin C and E increased. In contrast, in callus treated with SWSP the amount of glucose and fructose increased as well as all the antioxidant activities. The data evidenced that HS rich in tartaric and fatty acids had beneficial effects on callus growth contrary to soil water-soluble phenols rich in aldehydes, and syringic, ferulic, and benzoic acids.

Two liquid protein hydrolysates obtained from chickpea (Cicer arietinum L.) (CA) and Spirulina platensis (SP) were analyzed via FT-IR and SERS spectroscopy. Their hormone-like activities and contents in indole-3-acetic acid (IAA), isopentenyladenosine (IPA), nitrogen (N), carbon (C), sulfur (S), phenols, amino acids, and reducing sugars were determined. CA and SP showed different chemical compositions in N, C, sugars, amino acid, and TP contents, which were generally higher in CA. The two products exhibited (IAA)-like and gibberellin (GA)-like activities and contained the hormones IAA and IPA. Specifically, CA held higher (∼3.6 fold) IAA-like activity than SP, while its GA-like activity was comparable to SP. The content in IAA was similar between hydrolysates, but CA contained ∼6 fold more IPA. CA and SP were further supplied at two different dosages (0.1 and 1 mL L) for 2 days to maize (Zea mays L.) plants grown in hydroponics. They positively influenced plant growth and accumulation of N-compounds (proteins, chlorophylls and phenols), with a more pronounced effect observed in plants treated with CA. Furthermore, they increased the activity of two enzymes, i.e., peroxidase and esterase, which are established markers for plant growth, differentiation and organogenesis-related processes. Peroxidase activity in particular, was enhanced by ~1.6 and ~2.3 fold in leaves and roots of CA-treated plants, respectively. Greater accumulation of macro (Ca, Mg, and K) and micro (Cu, Zn) elements was also evident in plants supplied with these products. In conclusion, our data indicate that both CA and SP exert positive effects in maize plants. However, CA appeared to be more efficient than SP to improve plant nutrition and growth parameters in some respects, likely by virtue of its higher content in phytochemicals (hormones, phenols, amino acids, reducing sugars) that may act as signaling molecules, and more pronounced IAA-like activity.

The adsorption of humic substances on Ag nanoparticles (AgNPs) is of crucial environmental importance and determines the toxicity of these NPs and the structure of adsorbed organic matter. In this work, the adsorption of two standard soil and leonardite International Humic Substances Society humic acids was studied on AgNPs of different sizes, shapes (spherical and star-like), and interfacial chemical compositions. Surface-enhanced optical (Raman and fluorescence) spectroscopies were used to follow the specific chemical groups involved in this adsorption. By means of the latter optical techniques, information regarding the binding mechanism and the macromolecular aggregation can be deduced. The influence of the surface chemical composition induced by the different functionalizations of the interfaces of these NPs is highly important regarding the chemical interactions of these complex organic macromolecules. The surface functionalization with positively charged alkyl diamines led to a large increase in the adsorption as well as a strong structural rearrangement of the macromolecule once adsorbed onto the surface.

Two biostimulants, one derived from alfalfa plants (AH) and the other obtained from red grape (RG), were chemically characterized using enzyme linked immuno-sorbent assays, Fourier transform infrared (FT-IR) and Raman spectroscopies. Two doses (50 and 100 mL L-1 for RG, and 25 and 50mL L-1 for AH) of biostimulants were applied to Capsicum chinensis L. plants cultivated in pots inside a tunnel. The experimental design consisted of the factorial combination of treatment (no biostimulant, plus AH, plus RG) at three doses (zero, low, and high) and two time-course applications (at the second and fourth week after transplantation) and the effects were recorded at flowering and maturity. Both biostimulants contained different amounts of indoleacetic acid and isopentenyladenosine; the AH spectra exhibited amino acid functional groups in the peptidic structure, while the RG spectra showed the presence of polyphenols, such as resveratrol. These results revealed that at flowering, RG and AH increased the weights of fresh leaves and fruits and the number of green fruits, whereas at maturity, the biostimulants most affected the fresh weight and number of red fruits. At flowering, the leaves of the treated plants contained high amounts of epicatechin, ascorbic acid, quercetin, and dihydrocapsaicin. At maturity, the leaves of the treated plants exhibited elevated amounts of fructose, glucose, chlorogenic, and ferulic acids. Moreover, green fruits exhibited a high content of chlorogenic acid, p-hydroxybenzoic acid, p-coumaric acid and antioxidant activity, while both AH- and RG-treated red fruits were highly endowed in capsaicin. The 1H high-resolution magic-angle spinning (HRMAS)-nuclear magnetic resonance (NMR) spectra of red fruits revealed that both products induced a high amount of NADP+, whereas RG also increased glucose, fumarate, ascorbate, thymidine and high molecular weight species. Our results suggested that AH and RG promoted plant growth and the production of secondary

A study of the interaction between paraquat (methyl viologen) and humic acids, extracted from a soil amended over 30 years with crop residues, cow slurries and cattle manure, was carried out by two emission spectroscopies based on plasmonic effects: surface-enhanced Raman scattering (SERS) and surface-enhanced fluorescence (SEF). To carry out this study Ag nanoparticles were used. The complex formation was tested by analyzing the effect of the herbicide on humic acids, and by varying experimental parameters such as the pH and the laser excitation wavelength. The study of the vibrational bands led to infer information about the interaction mechanism of paraquat with humic acids and to find a correlation between this interaction and the humic acids structural modification induced by the different amendments added to soil. © 2011 Elsevier B.V.

Charcoal is mainly composed by aromatic C but is characterized by several degrees of aromaticity, which complicate its identification and quantification in natural environments by conventional analyses. Charcoal is an almost ubiquitous component of soil, although often occurring in minor amounts. Hence, there is a great interest in studying the charcoal structure and understanding the behavior of charcoal in soils. In soil, it has been demonstrated that the chemical structure of charcoal is also dependant on its particle-size. In this paper we have applied infrared, normal Raman, SERS and SEF spectroscopies to study four size-fractions of charcoal (>2 mm, 2-1 mm, 1-0.5 mm and <0.5 mm) and their alkaline extracts from a burnt Pinus pinea forest. Second derivative FT-IR in agreement with the normal Raman spectroscopy have given information about the size of aromatic rings and the nature of substituted groups in size-fractions of charcoal. Carbon cluster size progressively decreased in the smallest fractions suggesting that higher graphitization and crystallization occurred in the coarsest fraction (>2 mm). The presence of organic N was well evidenced by the vibration of iso-cyanate and cyanamide groups in the fractions. This result is of great environmental importance because N may be immobilized in form of stable molecules like N-heterocyclic poliaromatic structures, and so persists in soils. The soluble organic C (SOC) extracted from charcoal size-fractions did not differ from the bulk charcoal in terms of IR and Raman spectra. Instead SERS and SEF provided further information regarding the ratio between the aromatic component and the aliphatic cross-linking one in studied fractions. © 2011 Elsevier B.V. All rights reserved.

Charcoal added to soil by wildfires is usually considered to be part of the most stable pool of soil organic matter (SOM). It consists of a continuum of slightly burned plant residues to completely charred material. We sampled the macroscopic charcoal pool produced by a moderate intensity wildfire in a pine coastal forest in Tuscany (Central Italy) with the aim of assessing the relationship between its particle size and chemical composition as well as its reactivity. Our conceptual approach included particle size separation by dry sieving and analysis of four size fractions (>2mm, 2-1mm, 1-0.5mm and <0.5mm) for elemental composition. The composition of the charcoal fractions was studied using solid-state 13C nuclear magnetic resonance (NMR) spectroscopy, diffuse reflectance Fourier transform infrared (DRIFT) spectroscopy, analytical pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) and CuO oxidation. The reactivity of the fractions was assessed using acid dichromate oxidation, while the morphology was observed using scanning electron microscopy (SEM). There were clear differences in chemistry and reactivity between the fractions. The different fractions are probably the result of both type of original plant material and the fire conditions. In fact, wood-derived charcoal largely prevalent in the largest fraction, while pine needles and herbs were most probably precursors of charcoal in the smallest fractions. The degree of charring was greatest for the coarse fraction, which represented 56% of the total charcoal, and decreased gradually to the finest fraction. The composition was completely aromatic for the coarsest fraction, whereas the finest fraction showed a greater contribution from aliphatic C- and N-containing components. The greatest reactivity was found for the smallest fraction, which represented 24% of the total charcoal. It is particularly rich in N and potentially susceptible to microbial decomposition. The study demonstrates that properties of